The present invention relates to a composition which comprises a pesticidal active compound combination, a method of controlling pests with this composition, a process for the preparation of the composition, its use and plant propagation material treated with it, and the use of a compound of the following formula (A) for the preparation of the composition.
Certain mixtures of active compounds are proposed for pest control in the literature. However, the biological properties of these mixtures of known compounds are not completely satisfactory in the field of pest control, and for this reason there is a need to provide further mixtures having synergistic pest control properties, in particular for controling of insects and representatives of the order Acarina. This object is achieved according to the invention by providing the present composition.
The invention accordingly relates to a composition for controlling insects or representatives of the order Acarina, which comprises a combination of variable amounts of one or more compounds of the formula 
in which
A is an unsubstituted or, depending on the possibility of substitution on the ring system, mono- to tetrasubstituted, aromatic or non-aromatic monocyclic or bicyclic heterocyclic radical, in which the substituents of A are chosen from the group consisting of C1-C3alkyl, C1-C3alkoxy, halogen, halo-C114 C3alkyl, cyclopropyl, halocyclopropyl, C2-C3alkenyl, C2-C3alkynyl, halo-C2-C3alkenyl, halo-C2-C3alkynyl, halo-C1-C3alkoxy, C1-C3-C3alkylthio, halo-C1-C3alkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro;
R is hydrogen, C1-C6alkyl, phenyl-C1-C4alkyl, C3-C6cycloalkyl, C2-C6alkenyl or C2-C6alkynyl; and
X is Nxe2x80x94NO2 or Nxe2x80x94CN,
in the free form or in salt form, if appropriate tautomers, in the free form or salt form, and one or more of the compounds:
and at least one auxiliary.
The compounds of the formula (A) are described in EP-A-580553.
(I) S-6-chloro-2,3-dihydro-2-oxo-1,3-oxazolo[4,5-b]pyridin-3-ylmethyl O,O-dimethyl phosphorothioate (azamethiphos) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 44;
(II) 2-chloro-1-(2,4-dichlorophenyl)vinyl diethyl phosphate (chlorfenvinphos) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 174;
(III) (RS)-xcex1-cyano-3-phenoxybenzyl (1RS)-cis-trans-3-(2,2-dichlorvinyl)-1,1-dimethylcyclo-propanecarboxylate (cypermethrin, cypermethrin high-cis) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 208;
(IV) N-cyclopropyl-1,3,5-triazine-2,4,6-triamine (cyromazin) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 217;
(V) 1-tert-butyl-3-(2,6-diisopropyl-4-phenoxyphenyl)thiourea (diafenthiuron) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 294;
(VI) O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl-phosphorothioate (diazinon) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 243;
(VII) 2,2-dichlorovinyl dimethyl phosphate (dichlorvos), is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 259;
(VIII) (E)-2-dimethylcarbamoyl-1-methylvinyl dimethyl phosphate (dicrotophos) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 322;
(IX) 5-cyano-2-cyclopropylamino-4,6-diaminopyrimidine (dicyclanil) is known from EP-A-244360;
(X) ethyl 2-(4-phenoxyphenoxy)ethylcarbamate (fenoxycarb) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 375;
(XI) 1-[4-chloro-3-(3-chloro-5-trifluoromethyl-2-pyridylox)phenyl]-3-(2,6-difluorobenzoyl)-urea (fluazuron) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 475;
(XII) butyl 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N,Nxe2x80x2-dimethyl-N,Nxe2x80x2-thiodicarbamate (furathiocarb) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 448;
(XIII) O-5-chloro-1-isopropyl-1H-1,2,4-triazol-3-yl O,O-diethyl phosphorothioate (isazofos) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 502;
(XIV) O-2,5-dichloro-4-iodophenyl O,O-dimethylphosphorothioate Godfenphos) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 1102;
(XV) prop-2-ynyl (xc2x1) (E,E)-3,7,11-trimethyidodeca-2,4-dienoate (kinoprene) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 1102;
(XVI) (R,S)-1-[2,5-dichloro-4-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-3-(2,6-difluorobenzoyl)-urea (lufenuron) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 628;
(XVII) methyl (E)-3-(dimethoxyphosphinothioyloxy)-2-methylacrylate (methacriphos) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 562;
(XVIII) S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl O,O-dimethyl phosphorodithioate (methidathion) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 567;
(XIX) dimethyl (E)-1-methyl-2-(methylcarbamoyl)vinyl phosphate (monocrotophos) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 597;
(XX) b 2-chloro-2-diethylcarbamoyl-1-methylvinyl dimethyl phosphate (phosphamidon) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 679;
(XXI) O-4-bromo-2-chlorophenyl O-ethyl S-propyl phosphorothioate (profenofos) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 705;
(XXII) a mixture of 50 to 80% of (2RS,4SR)-4-(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl phenyl ether and 50 to 20% of (2RS,4RS)-4-(2-ethyl-1,3-dioxolan-4-ylmethoxy)phenyl phenyl ether (diofenolan) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 363;
(XXIII) a substance obtainable from the Bacillus thuringiensis strain GC91 or a substance obtainable from the Bacillus thuringiensis strain NCTC11821 is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 62;
(XXIV) 2,3,4,5-tetrahydro-3-oxo-4-[(pyridin-3-yl)-methyleneamino]-6-methyl-1,2,4-triazine (pymetrozine) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 868; and
(XXV) isopropyl 4,4xe2x80x2-dibromobenzilate (bromopropylate) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 99,
(XXVI) isopropyl (E,E)-(R,S)-11-methoxy-3,7,11-trimethyldodeca-2,4-dienoate (methoprene) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 680;
(XXVII) O,O-diethyl S-2-ethylthioethyl phosphorodithioate (disulfuton) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 372;
(XXVIII) O,O-diethyl O-quinoxalin-2-yl phosphorothioate (quinalphos) is known from The Pesticide Manual, 10th Edition (1994), The British Crop Protection Council, London, page 890, and
(XXIX) (RS)-xcex1-cyano-3-phenoxybenzyl N-(2-chloro-xcex1,xcex1,xcex1-trifluoro-p-tolyl)-D-valinate (tau-fluvalinate) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 428.
(XXX) N,N-dimethyl-1,2,3-trithian-5-yl-amine (thiocyclam) is known from The Pesticide Manual, 9th Edition (1991), The Britsh Crop Protection Council, London, page 816; and
(XXXI) S-2-ethylthioethyl O,O-dimethyl phosphorodithioate (thiometon) is known from The Pesticide Manual, 9th Edition (1991), The British Crop Protection Council, London, page 819.
The compounds of the formula (A) can in some cases be in the form of tautomers. For example, if R is hydrogen, corresponding compounds of the formula (A), i.e. those having a 3-H-4-imino-perhydro-1,3,5-oxadiazine partial structure, can be in equilibrium with the respective tautomers which contain a 4-amino-1,2,5,6-tetrahydro-1,3,5-oxadiazine partial structure. Compounds of the formula (A) above and below are accordingly also to be understood as meaning, where appropriate, corresponding tautomers, even if the latter are not mentioned specifically in each case.
Compounds of the formula (A) which contain at least one basic centre can form, for example, acid addition salts. These are formed, for example, with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrogen halide acid, with strong organic carboxylic acids, such as C1-C4alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as dicarboxylic acids which are saturated or unsaturated, for example oxalic, malonic, succinic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Compounds of the formula (A) with at least one acid group can furthermore form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or trihydroxy-lower alkylamine, for example mono-, di- or triethanolamine. If appropriate, corresponding inner salts can furthermore be formed. Agrochemically advantageous salts are preferred in the context of the invention. As a result of the close relationship between the compounds of the formula (A) in the free form and in the form of their salts, the free compounds of the formula (A) and their salts above and below are also appropriately and expediently to be understood as meaning, where appropriate, the corresponding salts and the free compounds of the formula (A). The same applies correspondingly to tautomers of compounds of the formula (A) and salts thereof. In each case the free form is in general preferred.
Compositions which comprise the compound of the formula (A) in the free form are preferred in the context of the present invention.
The general terms used above and below have the meanings given below, unless defined otherwise.
Heteroatoms in the cyclic base structure of the heterocyclic radical R are all elements of the Periodic Table which can form at least two covalent bonds. N and S are preferred.
Halogenxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of haloalkyl, haloalkylthio, haloalkoxy, halocyclopropyl, haloalkenyl, haloalkynyl, haloallyloxy and haloallylthioxe2x80x94is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine, in particular chlorine.
Unless defined otherwise, carbon-containing groups and compounds in each case contain 1 up to and including 6, preferably 1 up to and including 3, in particular 1 or 2, carbon atoms.
Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably cyclopropyl.
Alkylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of phenylalkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthioxe2x80x94is, in each case taking into due consideration the number of carbon atoms contained from case to case in the corresponding group or compound, either straight-chain, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
Alkenyl, haloalkenyl, alkynyl and haloalkynyl are straight-chain or branched and in each case contain two or preferably one unsaturated carbon-carbon bond(s). The double or triple bonds of these substituents are preferably separated from the remaining part of the compound of the formula (A) by at least one saturated carbon atom. Examples are allyl, methallyl, but-2-enyl, but-3-enyl, propargyl, but-2-ynyl and but-3-ynyl.
Halogen-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkylthio, haloalkoxy, halocyclopropyl, haloalkenyl, haloalkynyl, haloallyloxy and haloallylthio, can be partly halogenated or perhalogenated, and in the case of multiple halogenation, the halogen substituents can be identical or different. Examples of haloalkylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of haloalkylthio and haloalkoxyxe2x80x94are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF2 or CF3; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCl3, CF2CHCl2, CF2CHF2, CF2CFCl2, CF2CHBr2, CF2CHClF, CF2CHBrF or CClFCHClF; propyl or isopropyl which is mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3, CF2CF2CF3 or CH(CF3)2; and butyl or one of its isomers which is mono- to nonasubstituted by fluorine, chlorine and/or bromine, such as CF(CF3)CHFCF3, CF2(CF2)2CF3 or CH2(CF2)2CF3. Examples of haloalkenyl are 2,2-difluoroethen-1-yl, 2,2- dichloroethen-1-yl, 2-chloroprop-1-en-3-yl, 2,3-dichloroprop-1-en-3-yl and 2,3-dibromoprop-1-en-3-yl. Examples of haloalkynyl are 2-chloroprop-1-yn-3-yl, 2,3-dichloroprop-1-yn-3-yl and 2,3-dibromoprop-1-yn-3-yl. Examples of halocyclopropyl are 2-chlorocyclopropyl, 2,2-difluorocyclopropyl and 2-chloro-2-fluoro-cyclopropyl. Examples of haloallyloxy are 2-chloroprop 1-en-3-yloxy, 2,3-dichloroprop-1-en-3-yloxy and 2,3-dibromoprop-1-en-3-yloxy. Examples of haloallylthio are 2-chloroprop-1-en-3-ylthio, 2,3-dichloroprop-1-en-3-ylthio and 2,3-dibromoprop-1-en-3-ylthio.
In phenylalkyl, an alkyl group bonded to the remaining part of the compound of the formula (A) is substituted by a phenyl group, the alkyl group preferably being straight-chain and the phenyl group preferably being bonded to the alkyl group in a position higher than the xcex1-position, in particular in the xcexa9-position; examples are benzyl, 2-phenylethyl and 4-phenylbutyl.
Particularly preferred compounds of the formula (A) are those in which
(1) R is hydrogen, C1-C4alkyl, C3-C6cycloalkyl, C2-C6alkenyl or C2-C6alkynyl, in particular H or CH3;
(2) the cyclic base skeleton of A contains 2 to 4, preferably conjugated, double bonds, preferably contains 2, preferably conjugated, double bonds, and in particular has aromatic character,
(3) the cyclic base skeleton of A contains 1 up to and including 4, in particular 1 up to and including 3, especially 1 or 2, heteroatoms, particularly preferably 2 heteroatoms;
(4) the cyclic base skeleton of A contains 1, 2 or 3 heteroatoms chosen from the group consisting of oxygen, sulfur and nitrogen, not more than one of the heteroatoms contained in the cyclic base skeleton being an oxygen or sulfur atom, preferably at least one nitrogen atom;
(5) a compound of the formula (A) in which A is mono or disubstituted by substituents chosen from the group consisting of halogen and C1-C3alkyl, in particular by halogen, especially by chlorine;
(6) a compound of the formula (A) in which the cyclic base skeleton of A is a pyridyl, 1-oxidopyridinio or thiazolyl group, preferably the cyclic base skeleton of A is a pyrid-3-yl-, 1-oxido-3-pyridinio or thiazol-5-yl group, in particular A is a pyrid-3-yl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-C1-C3alkylpyrid-5-yl, 1-oxido-3-pyridinio, 2-halo-1-oxido-5-pyridinio, 2,3-dihalo-1-oxido-5-pyridinio or 2-halothiazol-5-yl group, A is especially a pyrid-3yl, 2-halopyrid-5-yl, 2-halo-1-oxido-5-pyridinio or 2-halothiazol-5-yl group, preferably A is a 2-chloropyrid-5-yl, 2-methylpyrid-5-yl, 1-oxido-3-pyridinio, 2-chloro-1-oxido-5-pyridinio, 2,3-dichloro-1-oxido-5-pyridinio or 2-chlorothiazol-5-yl group, A is especially a pyrid-3-yl, 2-chloropyrid-5-yl, 2-chloro-1-oxido-5-pyridinio or 2-chlorothiazol-5-yl group, in particular A is a 2-chloropyrid-5-yl or, preferably, 2-chlorothiazol-5-yl group;
(7) a compound of the formula (A), in which X is Nxe2x80x94NO2;
(8) a compound of the formula (A), in which A is a 2-chlorothiazol-5-yl or 2-chloropyrid-5-yl group, R is C1-C4alkyl and X is Nxe2x80x94NO2.
Compounds of the formula (A) which are named as preferred in the context of the invention are
(A.1) 5-(2-chloropyrid-5-ylmethyl)-3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine;
(A.2) 5-(2-chlorothiazol-5-ylmethyl)-3-ethyl-4-nitroimino-perhydro-1,3,5-oxadiazine;
(A.3) 3-methyl-4-nitroimino-5-(1-oxido-3-pyridiniomethyl)-perhydro-1,3,5-oxadiazine;
(A.4) 5-(2-chloro-1-oxido-5-pydidiniomethyl)-3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine;
(A.5) 5-(2-chlorothiazol-5-ylmethyl)-3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine;
(A.6) 3-methyl-5-(2-methylpyrid-5-ylmethyl)-4-nitroimino-perhydro-1,3,5-oxadiazine;
(A.7) 3-(2-chloropyrid-5-ylmethyl)-4-nitroimino-perhydro-1,3,5-oxadiazine; and
(A.8) 3-(2-chlorothiazol-5-ylmethyl)-4-nitroimino-perhydro-1,3,5oxadiazine.
A composition which, in addition to the compound of the formula (A), comprises only one other pesticidally active compound (I) to (XXXI) is also preferred. A composition which comprises the compound 5-(2-chlorothiazol-5-ylmethyl)-3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine as active component (A) is likewise preferred. Compositions which, in addition to a compound of the formula (A), comprise azamethiphos, cypermethrin high-cis, fenoxycarb, diofenolan, profenofos or pymetrozine are furthermore preferred.
The active compound combination according to the invention preferably comprises the active compound of the formula (A) and one of the active compounds (I) to (XXXI) in a mixing ratio of 100:1 to 1:6000, in particular 1:50 to 50:1, in particular in a ratio of between 1:20 and 20:1, in particular between 10:1 and 1:10, especially between 5:1 and 1:5, particularly preferably between 2:1 and 1:2, and also preferably between 4:1 and 2:1, especially in the ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1;3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. These ratios are understood as meaning weight ratios on the one hand, but also molar ratios on the other hand.
It has now been found, surprisingly, that the combination of the active compound of the formula (A) or of one of its salts with one of the active compounds (I) to (XXXI) not only causes an additive increase in the action spectrum on the pests to be controlled, which is to be expected in principle, but also achieves a synergistic effect which extends the action limits of both preparations under two aspects:
On the one hand, the rates of application of the compound of the formula (A) and of the individual compounds (I) to (XXXI) are lowered for the same good action. On the other hand, the combined mixture also still has a high degree of pest control where the two individual substances have become completely inactive in the range of low rates of application. This allows on the one hand a considerable extension to the spectrum of pests which can be controlled, and on the other hand an increase in application reliability.
In addition to the actual synergistic action in respect of pesticidal activity, however, the compositions according to the invention also additionally have further surprising advantages which can likewise be described as synergistic in a broadened sense: thus, for example, it is possible to control pests which cannot be controlled or sufficiently effectively controlled with the individual compounds(A) or (I) to (XXXI), and the compositions according to the invention have a better toleration by plants, i.e. a reduced phytotoxicity, than the individual compounds (A) and (I) to (XXXI). The insects can furthermore be controlled in their various stages of development, which is not always the case with the individual compounds (A) and (I) to (XXXI), since these compounds can be used, for example, only as adulticides or only as larvicides against quite specific larval stages. In addition, combinations of the compound (A) with certain compounds (I) to (XXXI) show more favourable properties during grinding, mixing, storage and also spraying.
The compositions according to the invention are already valuable preventively and/or curatively at low rates of concentration in the field of pest control, while being tolerated by warm-blooded animals, fishes and plants, and have a very favourable biocidal spectrum. The compositions according to the invention are active against all or individual stages of development of normally sensitive and also resistant animal pests, such as insects and representatives of the order Acarina. The insecticidal and/or acaricidal action of the compositions according to the invention can manifest itself here directly, i.e. in a destruction of the pests, which occurs immediately or only after some time, for example during moulting, or indirectly, for example in a reduced oviposition and/or hatching rate, the good action corresponding to a rate of destruction (mortality) of at least 50 to 60%.
The animal pests include, for example:
from the order Lepidoptera
Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula spp., Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Uthocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;
from the order Coleoptera, for example
Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Oryzaephilus spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp.;
from the order Orthoptera, for example
Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.;
from the order Isoptera, for example
Reticulitermes spp.;
from the order Psocoptera, for example
Uposcelis spp.;
from the order Anoplura, for example
Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp;
from the order Mallophaga, for example
Damalinea spp. and Trichodectes spp.;
from the order Thysanoptera, for example
Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and Scirtothrips aurantli; 
from the order Heteroptera, for example
Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp. Eurygaster spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahibergetla singularis, Scotinophara spp. and Triatoma spp.;
from the order Homoptera, for example
Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidliotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma lanigerum, Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium comi, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylia spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; 
from the order Hymenoptera, for example
Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.;
from the order Diptera, for example
Aedes spp., Antherigona soccata, Biblo hortulanus, Calliphora erythrocephala, Ceratifis spp., Chrysomyia spp., Culex spp., Outerebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Hypodermna spp., Hyppobosca spp., Uriomyza spp., Lucitia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;
from the order Siphonaptera, for example
Ceratophyllus spp. and Xenopsylla cheopis; 
from the order Thysanura, for example
Lepisma saccharina and
from the order Acarina, for example
Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.
Using the active compound mixtures according to the invention, in particular pests of the type mentioned which occur on plants, especially useful plants and omamentals in agriculture, in horticulture and in forestry, or on parts such as fruit, blossom, foliage, stems, tubers, or roots, of such plants can be controlled, i.e. checked or destroyed; in some cases even parts of plants which grow later are still protected from these pests.
The pesticidal mixture according to the invention can advantageously be employed for pest control in cereals, such as maize or sorghum; in fruit, for example pome, stone and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries and blackberries; in leguminous plants, such as beans, lentils, peas or soya; in oil-bearing crops, such as oilseed rape, mustard, poppy, olive, sunflower, coconut, castor, cacao or groundnuts; in cucurbits, such as pumpkins, cucumbers or melons; in fibre plants, such as cotton, flax, hemp or jute; in citrus fruits, such as oranges, lemons, grapefruits or mandarins; in vegetables, such as spinach, lettuce, asparagus, cabbage varieties, carrots, onions, tomatoes, potatoes or capsicum; in laurareous plants, such as avocado, cinnamonium or camphor; or in tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, musaceous plant, natural rubber plants or ornamentals, in particular in maize, sorghum, pome and stone fruits, leguminous plants, gourds, cotton, citrus fruits, vegetables, aubergines, vines, hops or ornamentals, especially in maize, sorghum, apples, pears, plums, peaches, beans, peas, soya, olives, sunflowers, coconut, cacao, groundnuts, cucumbers, pumpkins, citrus fruits, cabbage varieties, tomatoes, potatoes, vines or cotton, particularly preferably in vines, citrus fruits, apples, pears, tomatoes and cotton.
Other fields of use of the active compound mixtures according to the invention are protection of stored products and stocks and of material, and in the hygiene sector, in particular the protection of domestic animals and productive livestock against pests of the type mentioned.
Depending on the aims to be achieved and the given circumstances, the pesticides according to the invention are emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, sprayable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances which comprise the compound of the formula (A) or one of its salts and one of the other active compounds (I) to (XXXI) according to the invention.
The active compounds are employed in these compositions in a pure form, the solid active compounds, for example, being employed in a specific particle size, or, preferably, together withxe2x80x94at leastxe2x80x94one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
Solvents are, for example: non-hydrogenated or partly hydrogenated aromatic hydrocarbons, preferably fractions C8 to C12 of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and ethers and esters thereof, such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or -ethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, non-epoxidized or epoxidized plant oils, such as non-epoxidized or epoxidized rapeseed, castor, coconut or soya oil, and silicone oils.
Solid carriers, for example for dusts and dispersible powders, which are as a rule used are natural rock powders, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silicic acids or highly disperse absorbent polymers can also be added to improve the physical properties. Granular, adsorptive granule carriers are porous types, such as pumice, crushed brick, sepiolite or bentonite, and non-adsorptive carrier materials are calcite or sand. A large number of granulated materials of inorganic or organic nature, in particular dolomite or comminuted plant residues, can furthermore be used.
Surface-active compounds are, depending on the nature of the active compound to be formulated, nonionic, cationic and/or anionic surfactants or surfactant mixtures having good emulsifying, dissolving and wetting properties. The surfactants listed below are to be regarded only as examples here; many other surfactants which are conventionally used in the art of formulation and are suitable according to the invention are described in the relevant literature.
Nonionic surfactants are, in particular, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols. Water-soluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide on polypropylene glycol, ethylenediaminopolypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain are furthermore suitable. The compounds mentioned usually comprise 1 to 5 ethylene glycol units per propylene glycol unit. Examples are nonylphenol-polyethoxyethanols, castor oil polyglycol ether, polypropylenelpolyethylene oxide adducts, trbutylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene-sorbitan, such as polyoxyethylene-sorbitan trioleate, are furthermore possible.
Cationic surfactants are, in particular, quaternary ammonium salts which contain, as substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower, non-halogenated or halogenated alkyl, benzyl or lower hydroxy alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethylammonium chloride and benzyldi(2-chloroethyl)ethylammonium bromide.
Suitable inorganic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds. Suitable soaps are the alkali metal, alkaline earth metal and substituted and unsubstituted ammonium salts of higher fatty acids (C10-C22), such as the sodium or potassium salts of oleic or stearic acid, or of naturally occurring fatty acid mixtures, which can be obtained, for example, from coconut oil or tall oil; and furthermore also the fatty acid methyltaurine salts. However, synthetic surfactants are more frequently used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates and sulfates are as a rule in the form of alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts, and in general contain an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals; examples are the sodium or calcium salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture prepared from naturally occurring fatty acids. These also include the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty acid radical having about 8 to 22 C atoms. Alkylarylsulfonates are, for example, the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, of dibutyinaphthalenesulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product. Corresponding phosphates, such as salts of the phosphoric acid ester of a p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids, are furthermore also suitable.
The compositions as a rule comprise 0.1 to 99%, in particular 0.1 to 95%, of a mixture of the active compound of the formula (A) with one of the active compounds (I) to (XXXI), and 1 to 99.9%, in particular 5 to 99.9%, ofxe2x80x94at leastxe2x80x94one solid or liquid auxiliary, where as a rule 0 to 25%, in particular 0.1 to 20%, of the compositions can be surfactants (% is in each case percent by weight). While concentrated compositions are rather preferred as commercial goods, the end user as a rule uses dilute compositions which have considerably lower active compound concentrations. Preferred compositions have, in particular, the following composition (%=percent by weight):
The compositions according to the invention can also comprise other solid or liquid auxiliaries such as stabilizers, for example non-epoxidized or epoxidized plant oils (for example epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilizers or other active compounds for achieving specific effects, for example bactericides, fungicides, nematicides, molluscicides or herbicides.
The compositions according to the invention are prepared in a known manner, in the absence of auxiliaries, for example, by grinding, sieving and/or pressing a solid active compound or active compound mixture, for example to a particular particle size, and in the presence of at least one auxiliary, for example, by intimate mixing and/or grinding of the active compound or active compound mixture with the auxiliary or auxilaries. The invention therefore also relates to a process for the preparation of the compositions.
Mixtures of a compound of the formula (A) with one or more of the compounds (I) to (XXXI) are preferably employed with the auxiliaries conventionally used in the art of formulation, and are therefore processed, for example, to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts and granules, and also to encapsulations in, for example, polymeric substances, in a known manner. The methods of application, such as spraying, atomizing, dusting, wetting, scattering or pouring are chosen, as is the nature of the composition, according to the aims to be achieved and the given circumstances.
The invention furthermore relates to the methods of application of the compositions, i.e. the methods of controlling pests of the type mentioned, such as spraying, atomizing, dusting, spreading, dressing, scattering or pouring, to be chosen according to the aims to be achieved and the given circumstances, and the use of the compositions for controlling pests of the type mentioned. Typical rates of concentration here are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active compound. The rate of application can vary within wide limits and depends on the nature of the soil, the nature of the application, (leaf application; seed dressing; application in the seed furrow), the crop plant, the pest to be controlled, the particular climatic circumstances which prevail and other factors determined by the nature of the application, the time of application and the target crop. The rates of application per hectare are in general 1 to 2000 g of active compound per hectare, in particular 10 to 1000 g/ha, preferably 20 to 600 g/ha.
A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), where the frequency of application and rate of application can be chosen according to the risk of infestation by the particular pest. However, the active compound can also enter the plants via the root system (systemic action) by impregnating the locus of the plants with a liquid composition or introducing the active compounds in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In paddy rice crops, such granules can be metered onto the flooded rice field.
The compositions according to the invention are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers, or grain, or plant seedlings, against animal pests. The propagation material can be treated with the composition before being brought out, for example seed can be dressed before sowing. The active compounds according to the invention can also be applied to the seed grains (coating) either by impregnating the grains in a liquid composition or coating them with a solid composition. The composition can also be applied to the site where the propagation material is brought out, during broadcasting, for example into the seed furrow during sowing. The invention furthermore relates to these treatment methods for plant propagation material and the plant propagation material treated in this way.
The following examples serve to illustrate the invention. They do not limit the invention.
Formulation examples (%=percent by weight, active compound ratios=weight ratios)
EO is the degree of ethoxylation of castor oil or tributylphenol.
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
The solutions are suitable for use in the form of tiny drops.
The active compounds are dissolved together in methylene chloride, the solution is sprayed onto the carrier and the solvent is then evaporated off in vacuo.
Intimate mixing of the carriers with the active compounds gives ready-to-use dusts.
The active compounds are mixed with the additives and ground thoroughly in a suitable mill. Wettable powders which can be diluted with water to give suspensions of any desired concentration are obtained.
Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.
Ready-to-use dusts are obtained by mixing the active compounds with the carrier and grinding the mixture on a suitable mill.
The active compounds are mixed with the additives and the mixture is ground and moistened with water. This mixture is extruded, granulated and then dried in a stream of air.
The finely ground active compounds are applied uniformly to the kaolin, which is moistened with polyethylene glycol, in a mixer. Dust-free coated granules are obtained in this way.
The finely ground active compounds are mixed intimately with the additives. A suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water is thus obtained.
It is often more practical to formulate the active compound of the formula (A) and one of the mixing partners (I) to (XXXI) individually and then to bring them together in the applicator in the desired mixing ratio as a xe2x80x9ctank mixxe2x80x9d in the water only shortly before application.
Biological Examples (%=percent by weight, unless stated otherwise)
A synergistic effect is always present if the action EA of the combination of an active compound of the formula (A) with one of the active compounds (I) to (XXXI) is greater than the sum of the action of the active compounds applied individually:
EA1 greater than X+Y (B)
However, the pesticidal action EA to be expected for a given combination of two pesticides can also be calculated as follows (cf. COLBY, S. R., xe2x80x9cCalculating synergistic and antagonistic response of herbicide combinationsxe2x80x9d, Weeds 15, Pages 20-22, 1967):                               EA          2                =                  X          +                                    Y              ⁡                              (                                  100                  -                  X                                )                                      100                                              (        C        )            
In this equation:
X=Percent mortality on treatment with the compound of the formula (A) at a rate of application of p kg per hectare compared with the untreated control (=0%).
Y=Percent mortality on treatment with a compound (I) to (XXXI) at a rate of application of q kg per hectare compared with the untreated control.
EA=Expected pesticidal action (percent mortality compared with the untreated control) after treatment with the compound of the formula (A) and a compound (I) to (XXXI) at a rate of application of p+q kg of active compound per hectare.
If the action actually observed is greater than the expected value EA, synergism exists.